CN109593464A - A kind of organic silicon rubber coating of room curing and high temperature resistant, preparation method and application - Google Patents
A kind of organic silicon rubber coating of room curing and high temperature resistant, preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of organic silicon rubber coatings of room curing and high temperature resistant, preparation method and application, the organic silicon rubber coating is prepared by organic silicon rubber material, the organic silicon rubber material is based on organosilicon macromolecule chain and reinforced filling, fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler, interaction mechanism between fiber, for room temperature curing needed for high-temperature resistant silicone thermal protection coating use, high temperature resistant, the rigors of the excellent combination properties such as strong mechanical performance, it designs and has used the hydroxy-end capped polysiloxanes macromolecule containing different functional groups, white carbon black reinforced filling after modification, fire-resistant oxidation resistant filler, the matching system of high temperature resistant anti-ablation filler and fiber, and match suitable polysilazane curing agent, simplify the formula design of high temperature resistant elastic coating, it reduces Use to the huge carbon forming agent of Effect on Mechanical Properties.
Description
Technical field
The present invention relates to a kind of room curing and high temperature resistant silicone rubber coatings and its preparation method and application, belong to resistance to height
Warm elastic material and its preparation technical field.
Background technique
With the fast development of modern aerospace demand, the flying speed of required aircraft is getting faster, and is made
The temperature that faces of aircraft is higher and higher, this just proposes increasingly higher demands to high temperature resistant protective materials, such as protects
The performances such as room temperature curing, high temperature resistant, the high mechanics of material.Traditional using resin base as the thermal protection coating of matrix, such as epoxy
Resinous coat, phenolic coating etc. are often limited due to its matter is crisp by application.And organic silicon rubber material is because it is with good
Preferred, but its mechanical property of the characteristics high temperature resistant such as good heat resistance, cold resistance, weatherability, ageing-resistant, high-toughness hot protective materials
Can be relatively poor, it is required to a large amount of reinforced filling and a certain amount of functional stuffing is cooperated to prepare, it is often strong in the high stretching of acquisition
The building-up property of its construction is lost while degree, adhesive strength mechanical strength, it is therefore desirable to it is excellent to develop a kind of comprehensive performance
Different silicone thermal protective materials.
Summary of the invention
In order to overcome the above problem, the present invention provides a kind of room curing and high temperature resistant silicone rubber coating and preparation side
Method and application, the organic silicon rubber coating can be with resistance to 500 DEG C or more high temperature, while having good processing performance, draftability
Can and adhesive property, moreover, the preparation method is simple, can after cold spraying construction technology room temperature curing at
Type, and preparation cost is low, prepares raw material with good processing performance.
The invention provides the following technical scheme:
The first aspect of the present invention provides a kind of room curing and high temperature resistant silicone rubber coating, and the coating is by having
Machine silastic material is prepared, and the organic silicon rubber material includes sizing component A, crosslinking and curing agent B component, wherein
Component A includes: basic glue, reinforced filling, fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler, fiber and solvent, the base
Plinth glue is hydroxy-end capped polysiloxanes；B component includes polysilazane and optionally catalyst；
The hydroxy-end capped polysiloxanes has the following structure:
In formula (1), R1And R2It is identical or different, it is independently from each other methyl, ethyl, phenyl, vinyl, itrile group, nitrile third
Base, x and y are the integer between 0~500, and are not simultaneously 0.
Preferably, in formula (1), x and y are the integer between 50~200.
Preferably, the molecular weight of the polysiloxanes is 1000~50000, and preferred molecular weight is 2000~30000.It is described
Polysiloxanes can form the cross-linked network of optimization, to ensure the mechanical property for the coating being prepared.In addition, by hydroxyl
Carbon containing organic group is introduced in the molecular structure of the polysiloxanes of base sealing end, is provided for coating blocking required at high temperature
" carbon source " has ensured the moulding processability and mechanical behavior under high temperature of coating to largely reduce the use of carbon forming agent.
Preferably, when the hydroxy-end capped polysiloxanes purification process, volatile content therein is in 1wt% or less.
According to the present invention, the reinforced filling is selected from white carbon black, and the white carbon black is modified dose of treated white carbon black.
For example, modified dose treated precipitated silica.Wherein, the precipitation method pass through silicic acid to be well known by persons skilled in the art
What the hydrolysis process of salt was prepared, there are a large amount of hydroxyls on surface.The modifying agent be silazane or silicone compounds,
Such as the combination of one or more of following modifying agent of 3wt%~15wt%: hexamethyldisilazane, pregnancy basic ring
Three silazane, hydrogeneous polysilazane, contain vinyl polysiloxane, polysilazane containing vinyl, prestox ring at hydrogen containing siloxane
Tetrasiloxane, hydroxyl polysiloxanes, containing hydrogen silicone oil, hydroxy silicon oil, vinyl silicone oil.
Using the precipitated silica after modifier treatment, the preparation cost of the component can be reduced, due to modification
The hydroxy radical content on white carbon black surface afterwards substantially reduces, and the organic silicon rubber material that not will lead to prepares coating generates viscosity play
Phenomena such as increasing, structuring, will not leading to the organic silicon rubber material, processing performance is deteriorated in the construction process, more will not shadow
Ring the heat resistance of coating.
According to the present invention, the fire-resistant oxidation resistant filler is selected from the processed rear inorganic compound with micro-nano structure
Composition, including variable valency metal oxide, rare earth oxide, specially di-iron trioxide, zinc oxide, tin oxide, oxidation
The group of one or more of titanium, molybdenum oxide, antimony oxide, cerium oxide, tungsten oxide, manganese oxide, nickel oxide, vanadium oxide etc.
It closes.
According to the present invention, the high temperature resistant anti-ablation filler be selected from it is processed after inorganic with lamella or hollow structure or
The composition of organic compound, specially sericite, sepiolite, illite, bentonite, expanded vermiculite, expanded perlite, slope thread
The combination of one or more of stone, graphene, carbon nanotube, glass hollow microballoon, phenolic aldehyde microballoon etc..
According to the present invention, the fiber is selected from glass fibre, quartz fibre, the Black Warrior after processing with micro-nano structure
The combination of one or more of rock fiber, carbon fiber, aramid fiber, pbo fiber etc..
According to the present invention, the solvent is selected from the combination of one or more of aliphatic hydrocarbon and aromatic hydrocarbon solvent, excellent
Select n-hexane, hexamethylene, petroleum ether, toluene, dimethylbenzene etc..
According to the present invention, the fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler and fiber are preferably through air-flow powder
Broken, screening, using the diameter or thickness obtained after surface modification treatment in 50 nanometers~500 micro particles.
The surface modification treatment is to be surface-treated using the combination of siloxanes or silazane or both, silicon used
Oxygen alkane, silazane are methyltrimethoxysilane, ethyl trimethoxy silane, methyltriethoxysilane, ethyl triethoxy
Silane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane,
Trifluoro propyl trimethoxy silane, trifluoro propyl triethoxysilane, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane,
The one or more of decamethylcyclopentaandoxane, octaphenylcyclotetrasiloxane, hexamethyldisilazane etc..The surface
The dosage of inorganic agent be the fire-resistant oxidation resistant filler of required processing, high temperature resistant anti-ablation filler or fiber quality 1wt%~
15wt%, preferably 3wt%~10wt%.
According to the present invention, in the B component, polysilazane is used as room temperature curing agent.The polysilazane is without spy
Other restriction can be known in the art polysilazane, illustratively, as disclosed in Chinese patent literature CN1101055A
Polysilazane；Also as applicant submit on the same day it is entitled " a kind of room temperature curing agent of organosilicon material resistant to high temperature,
The Chinese patent of preparation method and application ", is incorporated herein in its entirety in the application, as present disclosure.Preferably,
Preferably, the viscosity of the polysilazane at room temperature is 200~2000cps, preferably 500~1500cps.
Preferably, the molecular weight of the polysilazane is 200~60000, preferably 500~15000.
According to the present invention, in the B component, catalyst is selected from one of organotin or organic titanium compound or two
Kind or more combination, for example, dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins, two acetic acid
Dibutyl tin, dialkyl tin dimaleate, two mercaptan tin alkyls, mercaptan dioctyl tin, butyl titanate, the metatitanic acid tert-butyl ester,
The single compound of titanium acetylacetone etc. or its chelate, loaded article, preferably dibutyltin dilaurate, four fourth of metatitanic acid
The combination of one or more of ester, titanium acetylacetone.
According to the present invention, in the component A, each component has following mass parts ratio:
Hydroxy-end capped 100 mass parts of polysiloxanes, 15~45 mass parts of reinforced filling, fire-resistant oxidation resistant filler 3~
20 mass parts, 3~20 mass parts of high temperature resistant anti-ablation filler, 3~20 mass parts of fiber, 10~30 mass parts of solvent.
It is preferred that hydroxy-end capped 100 mass parts of polysiloxanes, 20~35 mass parts of reinforced filling, fire-resistant oxidation resistant filler
5~16 mass parts, 5~15 mass parts of high temperature resistant anti-ablation filler, 5~10 mass parts of fiber, 10~20 mass parts of solvent.
According to the present invention, in the B component, each component has following mass parts ratio:
100 mass parts of polysilazane, 0~5 mass parts of catalyst.
Preferably, in the B component, each component has following mass parts ratio:
100 mass parts of polysilazane, 0.1~2 mass parts of catalyst.
According to the present invention, in the rubber material, component A and component B have following mass parts ratio:
100 mass parts of component A, 1~12 mass parts of B component.
Preferably, in the rubber material, component A and component B have following mass parts ratio:
100 mass parts of component A, 2~8 mass parts of B component.
It according to the present invention, can be exemplary by being used under the conditions of room temperature curing, high temperature resistant after the silicone rubber coating spraying
Ground, at room temperature 1~7 day can completion of cure, can 1 at a high temperature of 500 DEG C or more~use for 24 hours；
According to the present invention, the tensile strength (testing standard GB/T 528) of the coating at room temperature is greater than 3.0MPa, breaks
Splitting elongation is 80-150%, and adhesive strength (testing standard GB/T 7124) is greater than 3.3MPa.It can be prepared by spraying process
The organic silicon rubber coating of 2~5mm thickness, the coating can tolerate 500 DEG C of high temperature for 24 hours, within mass loss 10%.
The second aspect of the present invention provides the preparation method of above-mentioned room curing and high temperature resistant silicone rubber coating, described
Method includes the following steps:
1) kneader or planet is added in the basic glue, reinforced filling, fire-resistant oxidation resistant filler that include in above-mentioned component A
Blender mixes 2~6h under 100~160 DEG C, the vacuum degree of 50~300Pa, and three-roll grinder is used to be kneaded 2~4 times；It will
Resulting material and the filler of high temperature resistant anti-ablation function, fiber are added in vertical kneading mixer, mix under the revolving speed of 5~20rpm
It closes uniform；Resulting material and solvent are added in batch mixer, mixed component A is prepared after dilution；
2) each component for including in above-mentioned B component is mixed, mixed B component is prepared；
3) when in use, component A and B component are respectively charged into two material pots of spray equipment, adjust metering pump
Revolving speed protects needed for being ejected under the dry air pressure auxiliary of 1~5MPa after mixing in the mixing chamber of spray equipment
The room curing and high temperature resistant silicone rubber coating is prepared at room temperature through 1~7 day curing molding in device surface.
According to the present invention, in step 1), the viscosity of the component A has fine at 30000~200000cps (25 DEG C)
Mobility, meet the requirement of various moulding process.
According to the present invention, it in step 2), is mixed preferably by mechanical stirring.
The third aspect of the present invention provides the application of above-mentioned room curing and high temperature resistant silicone rubber coating, is used to fly
The fields such as the thermal protection on the surfaces such as body, engine under row device high-speed flight, the high temperature resistant protection of gas turbine.
Beneficial effect
1. organic silicon rubber coating of the present invention is prepared by organic silicon rubber material, the organosilicon rubber
Glue material be based on organosilicon macromolecule chain and reinforced filling, fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler, fiber it
Between interaction mechanism, for room temperature curing, high temperature resistant, Gao Lixue needed for high-temperature resistant silicone thermal protection coating use
The rigors of the excellent combination properties such as performance design and have used the hydroxy-end capped polysiloxanes high score containing different functional groups
The matching body of white carbon black reinforced filling, fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler and fiber after son, modification
System, and suitable polysilazane curing agent is matched, it simplifies the formula design of high temperature resistant elastic coating, reduce to mechanical property
The use for influencing huge carbon forming agent, realize preparation high intensity, room temperature curing, eiastomeric silicone resin resistant to high temperature mesh
Mark, meets requirement.
2. hydroxy-end capped polysiloxanes provides the matrix material of organic silicone rubber coating, the hydroxyl and curing agent of sealing end
Form the basic cross-linked network of curing of coatings object；White carbon black reinforced filling assigns the high mechanical property of coating to organic silicon rubber reinforcement
Energy；The fire-resistant oxidation resistant filler of micro-nano structure assigns organic silicon rubber coating good inoxidizability under high temperature aerobic environment
Energy；Lamella or the high temperature resistant anti-ablation filler of hollow structure assign the good Burning corrosion resistance energy of organic silicon rubber coating；Fiber is assigned
Organic silicon rubber coating is given to prevent dusting when organic/inorganic conversion occurs under high temperature aerobic environment, promote solid charcoal；Poly- silicon nitrogen
Alkane curing agent assigns the room temperature curing of polysiloxanes and resists the degradation of polysiloxane molecule chain at high temperature by silazine link.This
Invention is exactly comprehensive to be matched using multinomial technology, forms room temperature curing, organic silicon rubber thermal protection coating resistant to high temperature.
3. particularly, having abandoned high-cost fume colloidal silica in reinforced filling of the invention, low cost has been used
Precipitated silica, and this precipitated silica divides because the essence of its hydrolysis process makes it contain a large amount of polysiloxanes that causes
The hydroxyl of subchain degradation, therefore be not used in the preparation of high temperature resistant polysilane generally.And the present invention by locating white carbon black in advance
Reason, and cooperate polysilazane curing agent, organic silicon rubber can be made using the precipitated silica of low cost by realizing
Coating obtains good high temperature resistance, and during the preparation process, additional aftertreatment technology is not needed, so that organosilicon rubber
The preparation process of glue material is easy, improves preparation efficiency, reduces production cost.
4. fire-resistant oxidation resistant filler of the invention, high temperature resistant anti-ablation filler and fiber all have passed through air-flow crushing, table
Face modification realizes good point of fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler, fiber in organic silicon rubber
It dissipates, and eliminates the hydroxyl isopolarity group for influencing high-temperature behavior, cooperate polysilazane curing agent, realize organic silicon rubber painting
The good thermal protective performance of layer.
Specific embodiment
As previously mentioned, shown in the structure of the polysilazane such as formula (2):
In formula (2), R1, R2, R3 are identical or different, are independently from each other H, methyl, ethyl, phenyl, vinyl, alkane
One or more, the integer that x, y are 5~1000 of oxygroup, the ratio of x, y are 1:0.2~1.5.
Preferably, the ratio of x, y are 1:0.5~1.2.
Wherein, the polysilazane is prepared by the ammonolysis technique of chlorosilane, and the chlorosilane is trichlorosilane, dichloro
Silane, methyl trichlorosilane, dimethyldichlorosilane, ethyl trichlorosilane, diethyl dichlorosilane, phenyl trichlorosilane, two
Diphenyl dichlorosilane, dichloromethyl phenylsilane, vinyl trichlorosilane, methylvinyldichlorosilane, methyl methoxy base two
Two or more in chlorosilane, methyl ethoxy dichlorosilane etc..
The preparation method of above-mentioned polysilazane, described method includes following steps:
(1) solvent, ammonia, two function chlorosilanes and trifunctional chlorosilane are dried, reaction unit is carried out
It is dried；
(2) solvent of drying process is added in reaction unit by metering pump, by two function chlorine silicon of drying process
Alkane and trifunctional chlorosilane are added in reaction unit by metering pump respectively, and the ammonia of drying process is led to by mass flowmenter
Under the liquid level for entering reaction unit, ammonolysis reaction is carried out；
(3) " slurry " system for containing a large amount of ammonium chlorides after reaction is squeezed by filter device by mortar pump, carried out
It filters and filter residue is washed using solvent, collect filtrate；
(4) being introduced containing the filtrate of polysilazane product by material shifting pump, there is the film of continuous still function to steam
Send out device in, under the vacuum of 50~1000Pa, 50~150 DEG C at a temperature of, the solvent in above-mentioned filtrate is divided exactly, institute is obtained
The polysilazane product needed.
In step (1), the drying process preferably using continuing through the drying modes of molecular sieve absorbents, by solvent,
The water content of ammonia, two function chlorosilanes and trifunctional chlorosilane is controlled in 5ppm hereinafter, wherein molecular sieve is after water suction saturation
It can be regenerated by high temperature sintering.
In step (1), the solvent is that aliphatic hydrocarbon or aromatic hydrocarbon and its any one or two kinds of of corresponding halogenated hydrocarbons mix
Bonding solvent, preferably toluene, petroleum ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether etc..
In step (2), the usage ratio of two function chlorosilanes and trifunctional chlorosilane can pass through the frequency conversion of control metering pump
Device is adjusted, and in 3000~8000rpm, the temperature of reaction unit is controlled at -40~100 DEG C for the speed of agitator control of reaction unit,
The time of ammonolysis reaction be 8~for 24 hours.
In step (2), during ammonolysis reaction, 3~10 ammonias are distributed around agitating shaft preferably in reaction unit
Outlet, and with the pressurized dry air of 1~10MPa, it assists ammonia to generate micro-nano bubble in exit, is strengthened by supercharging air
Ammonia forms micro-nano structure bubble, and then strengthens because the generation of a large amount of ammonium chlorides leads to ammonia in gas-liquid-solid reaction system
Dispersion increases ammonia and chlorosilane contact probability in gas-liquid-solid reaction system, improves reaction efficiency；It is also excellent
It is selected in reaction unit and places a certain number of Ceramic Balls, it is made to collide under the high-speed rotation of agitating device, destroy former
A large amount of ammonium chloride particles that position generates reduce the damage of polysilazane to the cladding of chlorosilane reactant, polysilazane product
It loses, improves reaction yield；Online ammonia detection device is installed in the exhaust outlet of reaction unit, is joined with the mass flowmenter of ammonia
It is dynamic, the uninterrupted of the mass flowmenter of ammonia is adjusted with the ammonia signal strength detected, optimizing process control.Just
It is to be improved based on preparation method, less trifunctional chlorosilane, which can be used, can prepare the poly- silicon with same solidification effect
Azane.Preferably, the control of the mass ratio of the two functions chlorosilane and trifunctional is in 1:0.2~1.5, preferably 1:0.5~1.2.
In step (3), during the filtration process, preferably the filter device with different filtering accuracies carries out multistage-combination, should
Combination unit is able to achieve the filter type of moisture in not ingress of air, the closed material of energy, as filtration washing all-in-one machine, centrifuge are made
For the coarse filter device of the first order, there is the PP cotton of refined filtration effect, ceramic core etc. to be used as second for setting in percolate collection tubes road
The fine filtration device of grade；Observation window is set in percolate collection tubes road, whether is clarified convenient for observation filtrate, if there is muddiness,
It is returned in filter device by the branch in percolate collection tubes road and is filtered again.
In step (4), in distillation process, thin film evaporator is preferably carried out to 2~3 grades of multistage-combination, with continuous
Mode rapid solvent removal, further, the thin film evaporation preferably built in condenser external thin film evaporator and condenser
The multistage-combination of device, wherein afterbody is the thin film evaporator built in condenser.
Further detailed description is done to preparation method of the invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Experimental method used in following embodiments is conventional method unless otherwise specified；
Reagent and material in following embodiments commercially obtain unless otherwise specified.
Preparation example 1
600L petroleum ether (30~60 DEG C of boiling point) is added after dry through metering pump to the reaction kettle of 1000L by molecular sieve
In, 100kg dimethyldichlorosilane, 100kg methyl trichlorine silicon are added into reaction kettle by the frequency control of metering pump respectively
Alkane starts the stirring of reaction kettle in 5000rpm, controls reactor temperature at -20 DEG C by refrigeration machine, ammonia is passed through molecule
Reaction kettle is entered by mass flowmenter control after sieve is dry, by 5 air inlets of arrangement 3MPa's around agitating shaft
Enter reaction system in a manner of microbubble under air pressure auxiliary, placed 10kg Ceramic Balls in reaction kettle, for breaking original
Cladding of the ammonium chloride that position generates to the poly- methylsilazane of dimethyldichlorosilane, methyl trichlorosilane and generation.Reactant
The logical ammonia of stopping passes through detection of the ammonia at tail gas during this ammonolysis after system can't detect ammonia in tail gas after 24h
The linkage control reaction process of value and ammonia feed rate.Pass through the filtration washing with 400 micron filter cloths after ammonolysis
All-in-one machine filters pressing under the pressure of 0.4MPa is filtered twice by the filter cake of generation using filters pressing again after 300L petroleum ether
The filtrate that obtained filtrate obtains after merging by the fine filtering that 500nmPP cotton carries out the second level.Filtrate is passed through into condenser
External thin film evaporator is under the vacuum degree of 1000Pa, after at room temperature can collecting most of petroleum ether as light component
It recycles, then gained heavy constituent is steamed gently by the thin film evaporator built in condenser under the vacuum degree of 100Pa, at 60 DEG C
The heavy constituent obtained after component is required polysilazane.The viscosity 600cps of products therefrom, yield 82%, molecular weight are
1100。
Embodiment 1
The component A (following part, that is, representation quality part) of room curing and high temperature resistant silicone rubber thermal protection coating:
(trade mark is 107 silicon rubber to methyl polysiloxane, and manufacturer is spark organosilicon, and viscosity 7000cps is that is, above-mentioned
R in formula (1)1And R2It is simultaneously selected from methyl) 100 parts, precipitated silica (trade mark 779, manufacturer are that Fujian is just contained) 25
Part, 6 parts of di-iron trioxide with micro-nano structure, 10 parts of tin oxide with micro-nano structure, the glass with hollow structure is empty
10 parts of heart microballoon, 10 parts of glass fibre, 10 parts of hexamethylene with micro-nano structure.
Preparation technology of coating process is as follows:
(1) to methyl polysiloxane used using molecular distillation apparatus the vacuum degree of 50Pa, 140 DEG C at a temperature of carry out
Purification process, the fugitive constituent of the methyl polysiloxane of gained after purification are 0.5%；
(2) surface cladding pretreatment is carried out using the hydroxy silicon oil of 6wt% to precipitated silica (779)；
(3) the methyl trimethoxy oxygroup silicon of 6wt% is used di-iron trioxide, tin oxide, glass hollow microballoon, glass fibre
Alkane is surface-treated；
(4) required material is weighed according to formula, it first will be at methyl polysiloxane, pretreated precipitated silica, surface
The di-iron trioxide of reason, tin oxide are added in kneader, mix 4h under 120 DEG C, the vacuum degree of 100Pa, three rollers is used to grind
Machine is kneaded 3 times；Resulting material and glass hollow microballoon, glass fibre are added in vertical kneading mixer, under the revolving speed of 10rpm
It is uniformly mixed；Resulting material and hexamethylene are added in batch mixer, required component A is obtained after dilution.
(5) polysilazane and dibutyl that the molecular weight of the preparation of preparation example 1 is 1100 are weighed according to the mass ratio of 100:1
Tin dilaurate obtains required B component through mechanical stirring after mixing.
(6) component A and B component are respectively charged into two material pots of spray equipment, adjust the revolving speed of metering pump, make it
The mass ratio for meeting component A and B component is 100:5, in the dry air pressure of 2MPa after mixing in the mixing chamber of spray equipment
Required silicone thermal protection is made at room temperature through 5 days curing moldings in the device surface protected needed for being ejected under power auxiliary
Coating, with a thickness of 4mm.
Prepared coating tensile strength 3.5MPa at room temperature, elongation at break 120%, adhesive strength (aluminium-aluminium)
3.9MPa.In 500 DEG C of Muffle furnace after ablation for 24 hours, ablation mass loss rate 7.8%, surface after ablation is complete, without powder
Change phenomenon.
Embodiment 2
The component A (following part, that is, representation quality part) of room curing and high temperature resistant silicone rubber thermal protection coating:
(trade mark is 108 silicon rubber to phenyl polysiloxane, and manufacturer is Shanghai Resin Factory, viscosity 8000cps, i.e., above-mentioned
R in formula (1)1And R2It is simultaneously selected from phenyl) 100 parts, 30 parts of precipitated silica (trade mark 142, manufacturer are Rhodia),
There are 10 parts of zinc oxide of micro-nano structure, there are 5 parts of cerium oxide of micro-nano structure, 10 parts of expanded vermiculite with hollow structure have
5 parts of the sericite of layer structure has 8 parts of quartz fibre of micro-nano structure, 15 parts of petroleum ether.
Preparation technology of coating process is as follows:
(1) to phenyl polysiloxane used using molecular distillation apparatus the vacuum degree of 50Pa, 160 DEG C at a temperature of carry out
Purification process, the fugitive constituent of the phenyl polysiloxane of gained after purification are 0.3%；
(2) surface cladding pretreatment is carried out using the containing hydrogen silicone oil of 8wt% to precipitated silica；
(3) to zinc oxide, cerium oxide, expanded vermiculite, sericite, quartz fibre, the phenyl trimethoxy silicon of 8wt% is used
Alkane is surface-treated；
(4) required material is weighed according to formula, it first will be at phenyl polysiloxane, pretreated precipitated silica, surface
The zinc oxide of reason, cerium oxide are added in planetary mixer, mix 4h under 140 DEG C, the vacuum degree of 60Pa, use three-roll grinder
It is kneaded 3 times；Resulting material and expanded vermiculite, sericite, quartz fibre are added in vertical kneading mixer, in the revolving speed of 15rpm
It is lower to be uniformly mixed；Resulting material and petroleum ether are added in batch mixer, required component A is obtained after dilution.
(5) the preparation method preparation by polysilazane disclosed in CN1101055A is weighed according to the mass ratio of 100:2
Molecular weight be 600 polysilazane and stannous octoate, obtain required B component after mixing through mechanical stirring.
(6) component A and B component are respectively charged into two material pots of spray equipment, adjust the revolving speed of metering pump, make it
The mass ratio for meeting component A and B component is 100:8, in the dry air pressure of 3MPa after mixing in the mixing chamber of spray equipment
Required silicone thermal protection is made at room temperature through 7 days curing moldings in the device surface protected needed for being ejected under power auxiliary
Coating, with a thickness of 3mm.
Prepared coating tensile strength 4.0MPa at room temperature, elongation at break 80%, adhesive strength (aluminium-aluminium)
3.7MPa.In 500 DEG C of Muffle furnace after ablation for 24 hours, ablation mass loss rate 8.9%, surface after ablation is complete, without powder
Change phenomenon.
Comparative example 1
For the preparation process of the coating in embodiment 1, difference is only that the fire-resistant oxidation resistant filler omitted in component A
Or at least one of high temperature resistant anti-ablation filler or fiber, the coating being prepared at room temperature tensile strength 2.5~
3.0MPa elongation at break 200-300%, 2.8~3.2MPa of adhesive strength.In 500 DEG C of Muffle furnace after ablation for 24 hours, table
There is different degrees of powder phenomenon-tion in face, and mass loss is 15%~30%.
According to embodiment 1,2 and comparative example 1 as can be seen that not adding fire-resistant oxidation resistant filler or high temperature resistant anti-ablation is filled out
When material or fiber, under coating can largely keep the elongation at break of organosilicon material itself, but its high temperature resistance is obvious
, there is dusting after high temperature ablation in drop.And in embodiment 1,2, fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler and fiber
Addition and specific structure polysiloxanes and precipitated silica collective effect, substantially increase the heat resistance of coating, and
It is still able to maintain good tensile strength and elongation at break in relatively large addition filling component, obtains high temperature resistance and power
Learn the preferable coating material of performance.
Claims (10)
1. a kind of room curing and high temperature resistant silicone rubber coating, wherein the coating is prepared by organic silicon rubber material
Arrive, the organic silicon rubber material includes sizing component A, crosslinking and curing agent B component, wherein component A include: basic glue,
Reinforced filling, fire-resistant oxidation resistant filler, high temperature resistant anti-ablation filler, fiber and solvent, the basis glue is hydroxy-end capped
Polysiloxanes；B component includes polysilazane and optionally catalyst；
The hydroxy-end capped polysiloxanes has the following structure:
In formula (1), R1And R2It is identical or different, it is independently from each other methyl, ethyl, phenyl, vinyl, itrile group, nitrile propyl, x
And y is the integer between 0~500, and is not simultaneously 0.
2. coating according to claim 1, wherein in formula (1), x and y are the integer between 50~200.
Preferably, the molecular weight of the polysiloxanes is 1000~50000, and preferred molecular weight is 2000~30000.Preferably,
When the hydroxy-end capped polysiloxanes purification process, volatile content therein is in 1wt% or less.
3. coating according to claim 1 or 2, wherein the reinforced filling is selected from white carbon black, and the white carbon black is through changing
Property agent treated white carbon black.The for example, modified dose obtained white carbon black that treated is prepared by the precipitation method.
The modifying agent is silazane or silicone compounds, for example, 3wt%~15wt% one of following modifying agent or
Two or more combinations: hexamethyldisilazane, hydrogen containing siloxane, hydrogeneous polysilazane, contains second at hexamethyl cyclotrisilazane
Alkenyl polysiloxanes, polysilazane containing vinyl, octamethylcy-clotetrasiloxane, hydroxyl polysiloxanes, containing hydrogen silicone oil, hydroxyl silicon
Oil, vinyl silicone oil.
Preferably, the fire-resistant oxidation resistant filler is selected from the composition of the processed rear inorganic compound with micro-nano structure,
Including variable valency metal oxide, rare earth oxide, specially di-iron trioxide, zinc oxide, tin oxide, titanium oxide, oxidation
The combination of one or more of molybdenum, antimony oxide, cerium oxide, tungsten oxide, manganese oxide, nickel oxide, vanadium oxide etc..
Preferably, the high temperature resistant anti-ablation filler is selected from the processed rear inorganic or organic compound with lamella or hollow structure
The composition of object, specially sericite, sepiolite, illite, bentonite, expanded vermiculite, expanded perlite, palygorskite, graphite
The combination of one or more of alkene, carbon nanotube, glass hollow microballoon, phenolic aldehyde microballoon etc..
Preferably, the fiber be selected from after processing with the glass fibre of micro-nano structure, quartz fibre, basalt fibre,
The combination of one or more of carbon fiber, aramid fiber, pbo fiber etc..
Preferably, the solvent is selected from one or both of aliphatic hydrocarbon and aromatic hydrocarbon solvent, preferably n-hexane, hexamethylene, stone
Oily ether, toluene, dimethylbenzene etc..
4. coating according to claim 1-3, wherein the fire-resistant oxidation resistant filler, high temperature resistant anti-ablation
Filler and fiber are preferably through air-flow crushing, screening, using the diameter or thickness obtained after surface modification treatment at 50 nanometers
~500 micro particles.
The surface modification treatment is to be surface-treated using the combination of siloxanes or silazane or both, silicon oxygen used
Alkane, silazane are methyltrimethoxysilane, ethyl trimethoxy silane, methyltriethoxysilane, ethyl triethoxy silicane
Alkane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, three
Fluoropropyl trimethoxy silane, trifluoro propyl triethoxysilane, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane, ten
The one or more of methyl cyclopentasiloxane, octaphenylcyclotetrasiloxane, hexamethyldisilazane etc..At the surface
Manage agent dosage be the 1wt% of the fire-resistant oxidation resistant filler of required processing, high temperature resistant anti-ablation filler or fiber quality~
15wt%, preferably 3wt%~10wt%.
5. coating according to claim 1-4, wherein in the B component, polysilazane is as room temperature curing agent
It uses.
Preferably, the viscosity of the polysilazane is 200~2000cps, preferably 500~1500cps.
Preferably, the molecular weight of the polysilazane is 200~60000, preferably 500~15000.
Preferably, shown in the structure of the polysilazane such as formula (2):
In formula (2), R1, R2, R3 are identical or different, are independently from each other H, methyl, ethyl, phenyl, vinyl, alkoxy
One or more, the integer that x, y are 5~1000, the ratio of x, y is 1:0.2~1.5.
Preferably, the ratio of x, y are 1:0.5~1.2.
Preferably, the polysilazane is prepared by the ammonolysis technique of chlorosilane, and the chlorosilane is trichlorosilane, dichloro silicon
Alkane, methyl trichlorosilane, dimethyldichlorosilane, ethyl trichlorosilane, diethyl dichlorosilane, phenyl trichlorosilane, hexichol
Base dichlorosilane, dichloromethyl phenylsilane, vinyl trichlorosilane, methylvinyldichlorosilane, methyl methoxy base dichloro
Two or more in silane, methyl ethoxy dichlorosilane etc..
Preferably, in the B component, catalyst is combined selected from one or both of organotin or organic titanium compound,
For example, dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins, dibutyltin diacetate, dioxane
Base tin dimaleate, two mercaptan tin alkyls, mercaptan dioctyl tin, butyl titanate, the metatitanic acid tert-butyl ester, titanium acetylacetone etc.
Single compound or its chelate, loaded article, preferably dibutyltin dilaurate, butyl titanate, in titanium acetylacetone
One or two kinds of combinations.
6. coating according to claim 1-5, wherein in the component A, each component has following mass fraction
Than:
Hydroxy-end capped 100 mass parts of polysiloxanes, 15~45 mass parts of reinforced filling, 3~20 matter of fire-resistant oxidation resistant filler
Measure part, 3~20 mass parts of high temperature resistant anti-ablation filler, 3~20 mass parts of fiber, 10~30 mass parts of solvent.
Preferably, hydroxy-end capped 100 mass parts of polysiloxanes, 20~35 mass parts of reinforced filling, fire-resistant oxidation resistant filler 5
~16 mass parts, 5~15 mass parts of high temperature resistant anti-ablation filler, 5~10 mass parts of fiber, 10~20 mass parts of solvent.
Preferably, in the B component, each component has following mass parts ratio:
100 mass parts of polysilazane, 0~5 mass parts of catalyst.
Preferably, in the B component, each component has following mass parts ratio:
100 mass parts of polysilazane, 0.1~2 mass parts of catalyst.
Preferably, in the rubber material, component A and component B have following mass parts ratio:
100 mass parts of component A, 1~12 mass parts of B component.
Preferably, in the rubber material, component A and component B have following mass parts ratio:
100 mass parts of component A, 2~8 mass parts of B component.
7. coating according to claim 1-6, wherein the stretching of the organic silicon rubber material at room temperature is strong
Degree is greater than 3.0MPa, elongation at break is greater than 150%, and adhesive strength is greater than 3.3MPa.It can be prepared into 2 by spraying process~
The organic silicon rubber coating of 5mm thickness, the coating can tolerate 500 DEG C of high temperature for 24 hours, within mass loss 10%.
8. the preparation method of the described in any item room curing and high temperature resistant silicone rubber coatings of claim 1-7, the method
Include the following steps:
1) kneader or planet stirring is added in the basic glue, reinforced filling, fire-resistant oxidation resistant filler that include in above-mentioned component A
Machine mixes 2~6h under 100~160 DEG C, the vacuum degree of 50~300Pa, and grinder is used to be kneaded 2~4 times；By resulting object
Material and the filler of high temperature resistant anti-ablation function, fiber are added in kneader, are uniformly mixed under the revolving speed of 5~20rpm；By gained
Material and solvent be added batch mixer in, mixed component A is prepared after dilution；
2) each component for including in above-mentioned B component is mixed, mixed B component is prepared；
3) when in use, component A and B component are respectively charged into two material pots of spray equipment, adjust the revolving speed of metering pump,
The device table protected needed for being ejected under the dry air pressure auxiliary of 1~5MPa after being mixed in the mixing chamber of spray equipment
The room curing and high temperature resistant silicone rubber coating is prepared at room temperature through 1~7 day curing molding in face.
9. preparation method according to claim 8, wherein in step 1), the viscosity of the component A 30000~
200000cps(25℃)；
Preferably, it in step 2), is mixed preferably by mechanical stirring.
10. the application of the described in any item room curing and high temperature resistant silicone rubber coatings of claim 1-7, is used for aircraft
The thermal protection on the surfaces such as body, engine, the high temperature resistant of gas turbine protect field.
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